The subject invention is directed to a sheet product which is useful as separator components for batteries and to improved batteries containing the formed separator. More specifically, the present invention is directed to a thin microporous sheet product composed of either a highly filled polymeric matrix or a low level filled (including unfilled) polymeric matrix having a porous support sheet embedded between the sheet product's first and second major surfaces and having an average pore size distribution across the thickness of the sheet product such that there is a gradient of nominal pore size increasing from each major surface towards the interior, central portion of the sheet product's thickness.
Membranes have been formed from various materials and used in various applications such as in ion exchange, osmotic and ultra filtration devices including desalinization, kidney dialysis, gas separation and other applications. Macro and microporous membranes have been used as a means of insulating and separating electrodes in battery devices. Each application provides an environment and a set of desired parameters which are distinct to the specific application.
Storage batteries have at least one pair of electrodes of opposite polarity and, in general, have series of adjacent electrodes of alternating polarity. The current flow between these electrodes is maintained by an electrolyte which may be acidic, alkaline, or substantially neutral depending upon the nature of the battery system. Separators are located in batteries between adjacent electrodes of opposite polarity to prevent direct contact between the oppositely charged electrode plates while freely permitting electrolytic conduction. Separator components have taken many forms. In a modern battery design, the separator is in the form of a thin sheet or film or more preferably, a thin envelope surrounding each electrode plate of one polarity.
It is generally agreed that one of the critical elements in a battery design is the separator component and, to be highly effective in the design, the separator should have a combination of features. The battery separator must be resistant to degradation and instability with respect to the battery environment, including the other battery components and the battery chemistry. Thus, the battery separator must be capable of withstanding degradation of strong acids (such as sulfuric acid commonly used in acid battery designs) or strong alkali (such as potassium hydroxide used in alkaline battery designs) and to do so under ambient and elevated temperature conditions. Further, the separator should also be of a thin and highly porous character to provide a battery of high energy density. Although battery separators of thick or heavy design have been utilized in the past, such materials detract from the overall energy density of the battery by reducing the amount of electrodes that can be contained in a predetermined battery configuration and size. Another criteria is that the battery separator must be capable of allowing a high degree of electrolytic conductivity. Stated another way an effective separator membrane must exhibit a low electrical resistance when in the battery. The lower the electrical resistance the better the overall battery performance will be. A still further criteria is that the separator should be capable of inhibiting formation and growth of dendrites. Such dendrite formation occurs during battery operation when part of the electrode material becomes dissolved in the electrolyte and, while passing through the separator, deposits therein to develop a formation which can, after a period of time, bridge the thickness of the separator membrane and cause shorting between electrodes of opposite polarity.
In addition to meeting the above combination of properties, it is highly desired to have a sheet product which is capable of exhibiting good physical properties of tensile strength, flexibility and ductility to withstand the handling and processing without developing imperfections and cracks which would cause the sheet product to be unsuitable as a battery separator. Meeting this criteria is contrary to some of the above described properties (i.e. thin and light weight material and high porosity to provide good conductivity). In providing envelope type separators, these physical properties must also be accompanied by the ability of the material to be sealable by heat, or other means to provide a pocket design. As part of the physical property requirements, the sheet product must be capable of being formed as a cohesive material which retains this property throughout its service life.
Various microporous membranes or sheet materials have been suggested for utilization as a battery separator. Separators conventionally used in present battery systems are formed of polymeric films which when placed in an electrolyte or an electrolyte system, are capable of exhibiting a high degree of conductivity while being stable to the environment presented by the battery system. The films include macroporous as well as microporous materials. The porosity permits transportation of the electrolyte. Examples of such separators include unfilled polyolefin sheets which have been stretched and annealed to provide microporosity to the sheet, such as is described in U.S. Pat. Nos. 3,558,764; 3,679,538; and 3,853,601. In addition, polyolefin separators which include filler materials are disclosed in U.S. Pat. Nos. 3,351,495 and 4,024,323. In general, such polymer/filler compositions are friable materials and tend to exhibit electrical resistance which does not permit the formation of a highly efficient, high energy battery system.
Polysulfones are a known class of polymers which have been used to form various types of membranes. Polysulfone membranes are of a substantially non-flexible physical form. They have been widely used in forming in various separation apparatus, such as osmotic and ultrafiltration devices. Separation membranes differ from and do not normally have the constraints such as described in U.S. Pat. Nos. 3,855,122 and 3,709,841 placed upon a battery separator. For example, separation membranes are normally anisotropic in configuration (that is, asymmetrical in surface configuration, are not required to be ultra thin, and do not have to provide a high void volume as desired for battery separator designs. Further, such separation membranes are not conventionally used in highly corrosive environments as is conventionally found in a battery nor do they undergo the high degree of handling and processing as is required in the assembly of a battery. It has been noted that U.S. Pat. No. 4,714,663 discloses the use of a cast polysulfone membrane which is free of tertiary hydrogen atoms as being useful in a zinc ferricyanide battery, as an ion-selective separation membrane. The polysulfone separator is used as a means for separating the two different electrolyte solutions of this particular battery design.
It is highly desired to have a battery separator which is capable of exhibiting very low electrical resistance while at the same time providing the combination of properties described above.